Electron mediator, electron mediator immobilized electrode, and biofuel cell using the electrode

• US 7,544,438 B2
• Filed: 03/23/2004
• Issued: 06/09/2009
• Est. Priority Date: 09/02/2003
• Status: Expired due to Fees

• Current Assignee: Sekisui Medical Company Limited (Sekisui)
• Original Assignee: Daiichi Pure Chemicals Co., Ltd.
• Inventors: Nishizawa, Matsuhiko, Fukasaku, Noboru, Matsue, Tomokazu, Kosuge, Jun-ichi
• Primary Examiner(s): Lilling; Herbert J.
• Application Number:
  US10/807,489
• Publication Number:
  US 20050049313A1
• Time in Patent Office: 1,904 Days
• Field of Search: None
• US Class Current: 429/401
• CPC Class Codes: C07C 235/78 the carbon skeleton containing rings
• CPC Class Codes: C07C 66/02 Anthraquinone carboxylic acids
• CPC Class Codes: H01M 8/16 Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y10S 435/817 Enzyme or microbe electrode

Abstract

An object of the present invention is to provide a highly functional mediator capable of smoothly proceeding electron transfer between an electrode and a biocatalyst based on the premise that the mediator excels in safety and cost and to provide an electrode and a cell with sufficient amount of such a mediator molecule immobilized efficiently and strongly. The present invention provides a mediator mediating electron transfer between an enzyme and an electrode and containing a quinone molecule derivative, in particular, a mediator containing a VK₃ derivative. In addition, the present invention provides an electrode and a biofuel cell to which those mediators are applied.

Claims

1. An electrode comprising

a mediator, said mediator comprising a quinone molecule derivative,

a crosslinking agent, and

a polymer or a biopolymer,

wherein

the quinone molecule derivative is a quinone molecule modified with at least one functional group bonded with (i) the polymer or the biopolymer or (ii) the crosslinking agent;

the mediator is immobilized through bonding of the at least one modified functional group of the quinone molecule derivative; and

the mediator mediates electron transfer between at least one enzyme and an electrode.

2. An electrode according to claim 1, wherein the at least one enzyme is immobilized.

3. An electrode according to claim 2, wherein the at least one immobilized enzyme is diaphorase.

4. An electrode according to claim 2 comprising at least two immobilized enzymes, wherein the at least two immobilized enzymes are diaphorase and dehydrogenase.

5. An electrode according to claim 4, wherein the dehydrogenase is glucose dehydrogenase.

6. An electrode according to claim 4 or 5, further comprising immobilized co-enzyme NADH.

7. An electrode according to claim 2 comprising the mediator and the enzyme immobilized on the electrode by a polymer and a crosslinking agent.

8. An electrode according to claim 7, wherein the polymer is polyvinylimidazole.

9. An electrode according to claim 7 or 8, wherein the crosslinking agent is polyethylene glycol diglycidyl ether (PEGDGE).

10. An electrode according to claim 1, used for one of a biofuel cell and a biosensor.

11. The electrode according to claim 1 wherein the quinone molecule derivative is a naphthoquinone molecule derivative.

12. The electrode according to claim 11 wherein the naphthoquinone molecule derivative is at least one naphthoquinone molecule chosen from the group consisting of a sodium anthraquinone-2-sulfonate (AQS) derivative and a 2-methyl-1,4-naphthoquionone (VK3) derivative.

13. The electrode according to claim 11, wherein the naphthoquinone molecule derivative is a 2-methyl-1,4-naphthoquinone (VK3) derivative.

14. The electrode according to claim 13, wherein the 2-methyl-1,4-naphthoquinone (VK3) derivative is 2-methyl-1,4-naphthoquinone (VK3) modified with at least one functional group, wherein the at least one functional group is capable of bonding with a polymer or an enzyme.

15. The electrode according to claim 14, wherein the at least one functional group is selected from the group consisting of an amino group, a carboxyl group, a chloroformyl group, a succinimide oxycarbonyl group, an alkyl metal sulfosuccinimide oxycarbonyl group, a pentafluorophenyl oxycarbonyl group, a p-nitrophenyl oxycarbonyl group, a hydroxyl group, a formyl group, a halogen group, a maleimide group, an isothiocyanate group, and an oxiranyl group.

16. The electrode according to claim 15, wherein the 2-methyl-1,4-naphthoquinone (VK3) derivative is modified with the at least one functional group at a 2-position and/or a 3-position of the naphthoquinone.

17. The electrode according to claim 16, wherein the 2-methyl-1,4-naphthoquinone (VK3) derivative is a 3-methyl-1,4-naphthoquinone modified with the at least one functional group at the 2-position of the naphthoquinone.

18. The electrode according to claim 17, further comprised of a spacer molecule between the functional group and the 2-position of the naphthoquinone.

19. The electrode according to claim 18, wherein the spacer molecule is selected from the group consisting of a hydrocarbon linear chain, a polyoxyethylene linear chain, a polyethylene glycol chain, and a polypropylene glycol chain.

20. The electrode according to claim 19, wherein the spacer molecule is a hydrocarbon linear chain alkyl group.

21. The electrode according to claim 14, wherein the 2-methyl-1,4-naphthoquinone (VK3) derivative is one or more kinds of a quinone molecule selected from the group consisting of 2-(3-carboxypropyl)-3-methyl-1,4-naphthoquinone (CPVK3) represented by the following formula (1), 2-{3-[N-(2-aminoethyl)aminocarbonyl]propyl}-3-methyl-1,4-naphthoquinone (AEACPVK3) represented by the following formula (2), and 2-(3-aminopropyl)-3-methyl-1,4-naphthoquinone (APVK3) represented by the following formula (3):

22. The electrode according to claim 21, wherein the 2-methyl-1,4-naphthoquinone (VK3) derivative is 2-(3-carboxypropyl)-3-methyl-1,4-naphthoquinone (CPVK3) represented by the following formula (1):

23. An electrode according to claim 1 comprising a polymer, wherein

the modified functional group of the quinone molecule derivative of the mediator is bonded to the crosslinking agent;

and

the crosslinking agent is bonded to the polymer.

24. An electrode according to claim 23, wherein

the quinone molecule derivative is a quinone molecule modified with an amino functional group;

the polymer comprises an imidazole functional group;

the crosslinking agent comprises at least two epoxy functional group;

the amino functional group of the quinone molecule derivative bonds with a first epoxy functional group of the crosslinking agent;

the imidazole functional group of the polymer bonds with the second epoxy functional group of the crosslinking agent;

the bonded mediator, crosslinking agent, and polymer form an insoluble gel; and

the insoluble gel is immobilized on the electrode.

25. An electrode according to claim 23, wherein the polymer is polyvinylimidazole.

26. An electrode according to claim 23, wherein the crosslinking agent is polyethylene glycol diglycidyl ether (PEGDGE).

27. An electrode apparatus comprising

an electrode with an electrode surface;

a mediator comprising a quinone molecule derivative consisting of 2-(3-carboxypropyl)-3-methyl-1,4-naphthoquinone (CPVK3);

a diaphorase enzyme; and

a nicotinamide adenine dinucleotide molecule;

wherein

the mediator and the diaphorase enzyme are immobilized on the electrode surface by a polyvinylimidazole polymer and a polyethylene glycol diglycidyl ether (PEGDGE) crosslinking agent;

the immobilized diaphorase enzyme can catalyze electron transfer between the immobilized nicotinamide adenine dinucleotide molecule and the immobilized mediator; and

the immobilized mediator mediates electron transfer between the immobilized diaphorase enzyme and the electrode.

28. The electrode of claim 27 further comprising a dehydrogenase enzyme,

wherein

the dehydrogenase enzyme is immobilized on the electrode surface by the polyvinylimidazole polymer and the PEGDGE crosslinking agent;

the immobilized dehydrogenase enzyme can catalyze electron transfer between a biofuel and an oxidized form of the immobilized nicotinamide adenine dinucleotide molecule to form a reduced form of the immobilized nicotinamide adenine dinucleotide molecule; and

the immobilized diaphorase enzyme can catalyze electron transfer between the reduced form of the immobilized nicotinamide adenine dinucleotide molecule and the immobilized mediator.